Anti reflective coating, optical filter, optical lens, glasses lens, beam splitter, prisms, mirrors and other optical components and sanitary appliances in use to fingerprints, skin oils, sweat, cosmetics and other pollution. Once such a stain is difficult to be removed, especially in the light of an optical component attached to the anti reflective coating, and causing various problems.
In order to solve the problem, it has been proposed that the combination of inorganic materials (such as glass) and organic material called silane coupling technology. The silane coupling agent has an organic functional group or chemical structure with good affinity with the organic material in the molecule and has a reactive alkyl group. A self condensation reaction of the water in the air and the alkyl group of the alkyl group is formed by the self condensation reaction of the water in the air. At the same time, silane coupling agent with glass or metal surface to form chemical and physical bonds, which produces durable tough coating. Using these advantages, silane coupling agent is widely used as a coating agent for a variety of substrates.
Discloses application of chemical bonding in silane coupling agent in the introduction of fluorinated groups of compounds as a good film, and substrate adhesion and durability of the coating agent [Japanese patent Publication No. Zhao 58-167597, Japanese patent discloses no. Zhao 58-122979, 10-232301 and 2000-143991]. According to these patents, the introduction of the whole fluorine alkyl group on the substrate surface with silane coupling structure improves the fouling resistance (water repellent and oil repellent). But these compounds (molecular weight) due to enable perfluoro moieties length is limited, otherwise or if the perfluorinated moieties increased to long enough, alkoxy silyl in fluoride containing groups in the whole molecular proportion is relatively lower, resulting in adhesive or bonding durability deterioration, also does not have enough oil repellency. In order to solve these problems related to anti fouling, the technology of using various surface treatment compositions has been proposed. For example, Japan Patent Examination discloses the 1994 No. 29332 proposed the antifouling low reflective plastic, it has anti reflective coating on the surface, the anti reflective coating containing poly (fluoroalkyl methoxy silane and ethoxy silane compounds and halogen, alkyl or alkoxy silane compound. Recently, W02006/107083 presents a surface treatment composition comprising an organic silicon compound having an alkyl group at the end of a fluorocarbon chain. The surface treatment composition provides a low surface energy layer, which is adhered to the surface of various materials, especially the anti reflective film and other optical components and the glass surface. However, by now the method for the formation of antifouling coatings anti fouling property is not sufficient, especially, when the long-term use their resistance stain decreased significantly. Therefore, it is needed to develop an anti fouling coating with excellent fouling resistance and excellent durability.
However good smoothness of products is an important indicator of, the index is to the drops of water fall the inclination angle to define and excellent products sliding angle should be below 10 degrees is appropriate. At the same time, according to experience, with straight chain structure (Z type) of the product, due to the molecular chain of C-O content is higher than the side chain, with good flexibility.
The development of and improved anti fouling, scratch resistance and durability of antifouling coating composition products at the early stage of the development, the first research direction, hope to the tune of poly from perfluoro alkyl (such as Rf=C8F17) compounds (including perfluoroalkyl alkene and perfluoroalkyl based ethanol) as the starting material to synthesize corresponding to the following product.
RfC2H4-Si (OR)3 或 RfC2H4-Si (NR)3 (A1)
RfCH2CH2OCH2CH2CH2Si(OR)3 或 Rf CONHCH2CH2CH2Si(OR)3 (A2)
Hydrogen silane [H-Si (OR) and 3] (Rf-CH=CH2) perfluoroalkyl alkene addition reaction and A1 products. A2 and Dow products according to Daikin Corning patent (WO 2011/060047; CN 10266759 A) synthetic narrative method.
3M company of the United States Patent 5274159 described above second (A2) synthesis of compounds of formula structure and its application. Just to instances of the surface coating materials including C8F17C2H4-Si (NH) 3 / 2, C4F9C2H4Si (NH) 3 / 2 and poly silicon oxygen silazane (polysiloxazane) [the United States Patent No.4678688]. When these compounds are used alone, the friction durability becomes poor due to the lack of cross linking with the inorganic oxide substrate (substrate). So when only use this kind of fluorocarbon, did not obtain satisfactory antifouling properties. When using poly silicon oxygen silazane compounds, as a result of poly silicon oxygen silazane with larger than the fluorocarbon surface energy, initial anti fouling. In addition, due to the lack of the three-dimensional structure of the functional group formation, may cannot obtain sufficient chemical bonding to the substrate surface, resulting in durability testing, or use of, went to the treatment of the coating due to wipe the friction removed, causing the contact angle and resistance stain performance at a significantly lower, of course water repellent and oil proof also declined. Therefore, contaminants may accumulate or attach, and may leave fingerprints due to the low glass transition temperature. In the Japanese patent publication No.1990-233535 has silane compound perfluoro moieties as glass surface modifier, but the resulting coating showed no adequate water repellency, anti fouling and / or no pollution.
If tetrafluoroethylene (TFE) or hexafluoro propylene (HFP) does not contain oxygen atoms of the monomer, in under the action of the ultraviolet light catalysis and oxygen polymerization, and get the corresponding fluorine ether products. For example, Italy company (Ausimont) Osborne Monte is the use of this method in the production of FOMBLIN products - 60 C. Production of the corresponding products referred to as Z type (by TFE from straight chain type products) and Y type two (by HFP income containing CF3 side chain products), so resulting from the reaction of the crude product {there, N / m of the two types of the resultant ratio were 0.6 (Z type) and 0-0.1 (y)} by heat or light method to eliminate unstable over oxide groups and then fluorine of fluorination reaction (i.e. H / F exchange) to convert into stable end groups. Belongs to the Z type of Solvay Fomblin ZDOL-4000 (assuming required B-1 structure of raw materials, the molecular weight of 4000, and the value of n is 0. The m value is about 32.62}), but if you want to to Z-DEAL B-2 structure. (M and N of the average value is between 9 ~ 11) is with the following molecular structure PFPE pair of alcohol and diesters. That is the narrative responses generated corresponding fluorine ether products a good example::
HOCH2CF2O- (CF2CF2O) m- (CF2O) n-CF2CH2OH (B-1)
CH3O (O) CCF2O- (CF2CF2O) m- (CF2O) n-CF2C (O) OCH3 (B-2)
CH3O (O) CCF2O- (CF2CF2O) m-CF2C (O) OCH3 (B-3)
CF3O- (CF2CF2O) m- -CF2C (O) OC H3 (B-4)
CH3O (O) C (CF2) 3-O- (CF2CF2CF2CF2O) m- (CF2) 3C (O) OCH3 (B-5)
CF3CF2O- (CF2CF2O) m- (CF2O) n-CF2CH2OH (B-6)
If B1 as starting materials in accordance with Daikin and Dow Corning patent (Wo 2011/060047; CN a 10266759) patent system to the products, due to the presence of two of the two silicon alkyl, if the completion of the reaction, it is expected that there will be a better friction durability, bilateral to completely and the glass key nodes, steric hindrance, the general will have a certain number of only then unilateral, on the other side of the bare, caused by water contact angle affected, the highest can reach 108o. But due to the steric hindrance, steric none), the cause and the substrate chemical bonding coating interface may not be able to with the substrate to completely close, and smoothness are easily changed as a result of poor. Have corresponding method synthesis can depend on the U. S. patent 5488142 provides the B-3 and B-4 and B5 formula molecular structure of Fomblin F-PEO, F-MPEG and F-PTMO products. And 3M United States Patent 6277485 B1 is using these as B-3 and B-4 and B5 products as reaction initiator and 3-aminopropyl alkoxy silane 3-aminopropylalkoxysilanes generate may have instances of the corresponding products of antifouling coating effect. In addition, the B6 structure will also be the starting material to be considered.
Methyl ester compounds containing a CN; (patent and subsequent (FS 157 is about value, 157 DuPont lubricants having the following formula structure is mainly used in hard disk Krytox (belongs to K/Y structure the N 10, the average molecular weight of about 2000, this value should be said in Kansas with range lower limit), if C1 containing carboxyl group (- COOH) NaBH4 and LiAlH4 into corresponding CH2OH or directly into the methyl ester (Krytox L) former laws Daikin Dow Corning wo 2011/060047 10266759 reaction steps of the first and the allyl bromide reaction of unsaturated bond, and silicon hydrogen addition reaction, generate the final C2 products, while the latter is available
[KRYTOX 157 FS (L)] and the reaction of silane coupling agent containing amino and antifouling coating effect may have the corresponding C3 products are as follows:
C3F7O (CF (CF3) CF2O) nCF (CF3) COOH (C1)
C3F7O (CF (CF3) CF2O) nCF (CF3) CH2OCH2CH2 CH2Si (OR) 3 (C2)
C3F7O (CF (CF3) CF2O) nCF (CF3) CONH (CH2) 3Si (OR) 3 (C3)
Belongs to Daikin formula DEMNUM molecular structure of D type PFPE single alcohol structure: CF3CF2O - CF2CF2 (CF2O p-CF2CF2CH2OH (p=10.9) when the molecular weight of 2075; however if the required molecular weight is 4000, the required p value is about 22.5). The PFPE segments synthesis path will by tetrafluoroethylene (TFE) and melamine formaldehyde (internalization) resulting from the reaction of PTFE oxetane again after polymerization resulting from the reaction of the polymer, the fluorine gas fluorination get corresponding acyl fluoride ether. So from the acyl fluoride ether and NaBH4 and LiAlH4 reduction to the corresponding containing CH2OH functional group compounds, and then in the alkali catalyzed and first with allyl bromide reacts with unsaturated bonds compound, silicon hydrogen addition reaction, generate the final product.
Aims to Daikin and Dow Corning patent (Wo 2011/060047; a 10266759 CN narrative patent invention to solve the long-term use is resistant to contamination decreased significantly, providing with a formula following D type fluorine ether organosilicon surface treatment (D1) composition of preparation and use method. Using the generated compositions can be formed with high durability, excellent low surface energy processing layer, which prevents moisture or fingerprint, skin oils, sweat, cosmetics and other dirt attached to a variety of materials, especially used in antireflection film, optical components and glass on the surface of the water and dirt even in the posterior attachment can also easily be erased.
F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) p-X- (CH.) r-C3H6.Si (X) 3-A (R1) a (D1)
Among them, l is an integer of Q ~ 3; m, n and. Independently of 0 ~ 200 integer; P is 1 or 2; X is oxygen or a divalent organic group; and R is an integer from 0 to 17 of R1 is not with unsaturated aliphatic linkages straight chain or branched alkyl; a is an integer from 0 to 2; and X 'is independent of the choice of hydrolyzable groups. The composition consists of the following general formula (D2) and (D3) said the surface treatment composition does not contain reactive functional group is not with the substrate occurred chemical bonding fluorine containing compounds, the quality of its product quality pointer is the total content of this kind of material should be less than 25 mole% (but the best is below 20 mol%, in the surface processing.
F- (CF2) Q (OC3F6) m (OC2F4) n (OCF2) o-F (D2)
Q, m, N and o with the same,
F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) p-X- (CH2) r-CH=CHCH3 (D3)
Q, m, N, O, P, R and X with the same.
That is to say the desire in accordance with described the Daikin and Dow Corning patent product and preparation method, has good resistance to contamination and cool slip only containing single silane reaction based products. The process conditions requirements more stringent, the slightest mistake may output sub specifications of the products, so it is increase the process operational tolerance degree (tolerance) space needs.
Patent invention described in Korea Research Institute of Chemistry for the Korean patent (KR[31]10-2007-013094. Cn 101456947) hope to use polyfunctional amine, amide (polyfunctional aminoamide) as basic structure synthesis has the following general formula modified amino amide silane compounds, in order to solve the problems during long use is resistant to contamination decreased significantly.
Above n is 1 0 to 7 0 of the integer m is an integer from 1 to 3; P and Q independently of 2 or 3 R1 is C2-C4 alkyl; R2 and R3 independently for C1-C6 alkyl or phenyl; R4 is C3-C5 alkyl or C3-C6 alkyl ether; R5 is C1-C6 alkyl or phenyl; and X is a C1-C3 alkoxy. The composition of the present invention, although due to the increase in number of each member of the silane to obtain better treatment agent is chemically bonded to the substrate surface probability, resulting in contaminated resistance improved. But this product molecular design also has some shortcomings, first of all is to happen the Z and Y type structure may there is room for improvement, at the same time, the two silane groups placed side has a merit, but due to the three-dimensional structure is Pang pine bulky and stereo obstacles larger (steric hinder) amine based amide groups, multiple bond synthetic probability of reduce, the chemical bonding after treatment agent fragment and the substrate close may can not fully play, resulting in anti fouling performance improvement is unable to achieve the maximization.
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